Acyl hydrazones of 2,2,6,6-tetramethyl-piperidine-4-ones

ABSTRACT

ACYL HYDRAZONE DERIVATIVES OF 2,26,6-TETRAMETHYLPIPERIDINE-4-ONE ARE STABILIZERS OF ORGANIC MATERIALS. THEY ARE PREPARED BY REATING A CORRESPONDING ACID HYDRAZIDE WITH TRIA ONAMINE.

3,828,052 Patented Aug. 6, 1974 States Patent (Nice AB TRACT OF- THE DiscLosURE Ae 'r hydrazonederiv'atives ojf 2,2,6,6-tetramethylpiperidine-4-one arestabilizers 'of' organic materials. They are prepared by-racting a corresponding acid hydrazide with The present invention concerns new class of acyl hydrazone derivatives of 2,2,6 ,6 tetramethylpiperidine-4- one having value-as stabilisers for organic materials.

According to the present invention, there are provided compounds having the formula;

CCH2 CH, an, I and their acid salts wherein R represents hydrogen, a straightor branched alkyl residue having from 1 to 20, preferably from 1 to 17 more preferred from 1 to 12 carbon atoms in which the alkyl chain may be uninterrupted or interrupted by one or more, preferably one, sulphur atom, a cycloalkyl residue having from 5 to 12, preferably 6, carbon atoms, a cycloalkyl alkyl residue having from 6 to 12, preferably 7 to 11, carbon atoms, a phenyl residue, a naphthyl'r esidue, an aralkyl residue containing from 7 to 14, preferably 7 to 11, carbon atoms or an alkaryl residue preferably alkylphenyl having from 7 to 14, preferably 7 to 10, carbon atoms, or'R represents the grouping of formula:

wherein Y; is a divalentpstraight-or branched-chain alkylene residue having from 1'. to 20, preferably 1 to 10, more preferred 4 vto 10 carbon atoms, in which the alkylene chain is uninterrupted or interrupted by one or more, preferably-one,.. sulphur atom, or an arylene residue having from 6, to 12, preferably 6,. carbon atoms and a is 0 or, preferably, 1, orR represents the grouping having the III Examples of salts of piperidine derivatives (I) that can be used according to the invention include salts of an inorganic acid such as phosphates, carbonates, sulphates, chlorides" andthelikfe as"well a's organic acid salts such as citrates, acetatesfstea rates, male'ates, oxalates and benzo ate's'f" i I 25 Claims Examples of monovalent groups R are methyl, ethyl, n-

propyl, isopropyl, n-butyl, t-butyl, n-amyl, 2-ethylpropyl, n-hexyl, n-heptyl, n-octyl, n-undecyl, n-dodecyl, n-heptadecyl, n-octadecyl, eicosyl, fl-rnercaptoethyl, mercaptomethyl, fl-methylthioethyl, fi-octylthioethyl, aand 3-dodecylthioethyl, cyclopentyl, cyclohexyl, methylcyclohexyl, 4-t-butylcyclohexyl, cyclodecyl, adamantyl, 1- and 2-perhydronaphthyl, cyclopentylmethyl, cyclohexylmethyl," ficyclohexylethyl, land 2-(perhydronaphthyl) methyLB- [1- and 2-perhydronaphthyl]ethyl, benzyl, B-phenylethyl,

1- and 2-naphthylmethyl, 3-[1- and 2-naphthyl1ethyl, diphenylmethyl, 0-, mand p-tolyl, o-, mand p-ethylphenyl, 0-, mand p-isopropylphenyl, 6-, mand p-t-butylphenyl,

4 methyl-l-naphthyl, 4-ethyl-1-naphthyl, 4-isopropyl-1-' naphthyl and 4-t-butyl-l-naphthyl.

Examples of groups Y are methylene, 1,2-ethylene, 1,4- n-butylene, 1,8-n-octylene, 1,10-n-decy1ene, 1,2-eicosylene,

1,2-, 1,3- and 1,4-phenylene, 1,4- and 1,5-naphthylene, 4,4'--

However for the stabilisation of polyolefines, compounds of formula I having a high ratio of organophilic residue to secondary amine function are the most preferred on compatibility grounds. I v Specific examples of preferred compounds of formula Iare: 7

di-( 2,2,6,6-tetramethylpiperidinyl-4) adipoyl di-hydrazonei di-(2,2,6,6-tetramethylpiperidinyl-4) sebacoyl dihydrazone, I 1,.

di-(2,2,6,6-tetramethylpiperidinyl-4) thiodipropionyl di--" hydrazone, 2,2,6,6-tetramethylpiperidinyl-4-isocaproyl' 'hydrazone, 2,2,6,6-tetramethylpiperidinyI-4-heptanoyl hydra'zone,

n 2,2,6,6-tetramethylpiperidinyl-4-lauroyl hydrazone, f I j 2,2,6,6-tetramethylpiperidinyl-4-stearoyl hydrazone,"

3 2,2,6,6-tetramethylpiperidinyl-4-isobutyroyl hydrazone, 2,2,6,6-tetramethylpiperidinyl-4-benzoyl hydrazone, 2,2,6,6-tetramethylpiperidinyl-4-p-toluoyl hydrazone, 2,2,6,6-tetramethylpiperidinyl-4-a-naphthoyl hydrazone, 2,2,6,G-tetramethylpiperidinyl-4-phenylacetyl hydrazone, 2,2,6,G-tetramethylpiperidinyl-4-a-naphthylacetyl hydrazone,

2,2,6,6-tetramethylpiperidinyl-4-a,ot-diphenylacetyl hydrazone,

2,2,6,G-tetramethylpiperidinyl-4-cyclohexane carboxyl hydrazone,

di-(2,2,6,6-tetramethylpiperidinyl-4) isophthaloyl dihydrazone,

di-(2,2,6,6-tetramethylpiperidinyl-4) dodecane-l IO-dioyl di-hydrazone,

2,2,6,6-tetramethylpiperidinyl-4-p-t-butylbenzoyl hydrazlone, and

2,2,6,6-tetramethylpiperidinyl-4-2'-ethylhexanoyl hydrazone as well as the corresponding acid salts.

The present invention also provides a process in which the compound of formula I is produced comprising reacting an acid monohydrazide having the formula:

R-NHNH:

or an acid di-hydrazide having the formula:

HzN.HN-CI(Y)B(?NH.NH

wherein R and Y have their previous significance, with triacetonamine having the formula:

CH3 CH VI The reaction is conveniently eifected by heating the reactants together in a solvent inert to the reactants, for instance an aliphatic alcohol, ether, or aromatic hydrocarbon, especially methanol or ethanol, diethyl ether or toluene. Advantageously the reaction is conducted at the reflux temperature of the mixture using substantially equimolar proportions of each reactant. On completion of the reaction, the solid product may be isolated, and purified if desired, by conventional techniques.

The present invention still further provides a composition comprising an organic material and a minor proportion of a compound having the formula I as hereinbefore defined.

Compounds of formula I have been found to impart to polyolefines an exceptionally high degree of stability towards deterioration normally induced by the eifects of ultra-violet radiation. Moreover, this light stability is achieved without affecting the colour properties of the treated polyolefine. The stabilisers of the invention provide effective light and/or heat stabilisation especially for lowand high-density polyethylene and polypropylene and polystyrene as well as polymers of butene-l, pentene-l,

3-methylbutene-l, hexene-l, 4-methylpentene-1, 4-methylhexene-l and 4,4-dimethylpentene-l, as well as toand ter-polymers of olefines, particularly of ethylene or propylene. The compounds of formula I are particularly effective in stabilising polystyrene againstactinic radia tion.

Other organic materials susceptible to degradation by theeffects of light and the properties of which are improved by the incorporation therein of a compound of formula I include natural and synthetic polymeric materials, for instance natural and synthetic rubbers, the latter include, for example, homo-, coand terpolyrners of acrylonitrile, butadiene and styrene.

Specific synthetic polymers include polyvinyl *chloride and vinyl chloride co-polymers, polyvinyl acetate and as well as condensation polymers derived from ether, est ei" (ex carboxylic, sulphonic or carbonic acids), amide or urethane groupings. These polymers can, for instance, form the basis of surface coating media such as paints and lacquers having an oil or resin, for-instance an alkyd or polyamide resin, base.

The amount of the compound of formula I which is in-JI corporated into the organic material in order to achieve maximal protection against degradation by light varies according to the properties of the organic material treated and according to the severity of the light radiation and to the length of exposure. However, for most purposes it 'is' sufiicient to use an amount of the compound of formula I within the range of from 0.01% to 5% by Weight, more preferably within the range of from 0.1% to 2%, by weight based on the weight of untreated organic 'material.

Optionally, the composition of the invention may contain" further additives, especially those used in polyolefine form-v compound of formula I and thepolymer may be com pounded in an internal mixer. Alternatively, the compound of formula I may be added as a solution or slurry in a suitable solvent or dispersant, for instance an inert organic solvent such as methanol, ethanol or acetone to powdered polymer and the whole mixed intimately in a mixer, and the solvent subsequently removed. As a further alternative the compound of formula I may be added to the polymer.

during the preparation of the latter, for instancelat the latex stage of polymer production, to provide pre-stabilized polymer material.

Examples of suitable antioxidants are thoseof the bindered phenol type such as 2,6-ditertiarybutyl-p-cresol, 4,4- bis(2,d-ditertiarybutyl-phenol), 4,4,-bis(2,6 diisopropylphenol), 2,4,6-triisopropyl phenol, and 2,2-thio-bis(4-, methyl-G-tertiarybutylphenol) tetrakis [methylene-3 (3',5'-, dibutyl-4'-hydroxyphenyl) propionate] methane; esters of thiodipropionic acid, for example dilauryl.thiodipropionate; alkyl, aryl or alkaryl phosphites such as triphenyl phosphite, trinonyl phosphite and diphenyldecyl phosphite, and combinations of these antioxidants.

Further light stabilisers include those of the substituted benzotriazole class such as 2-(2' -hydroxy 5'-rnethyl) phenylbenzotriazole, 2-(2 hydroxy 3',5', di-t-butyl)-5- chlorophenyl-benzotriazole; those of the hydroxy benzophenone type; hindered phenols such as 2,4'-di-t-butyl phenyl -3,5-di-t-butyl-4-hydroxy benzoate and the stabilisers described in our copending British Patent Applications Nos. 18,090/70 and 28,063/70 and suitable metal complexants/deactivators include salicylidene-propylene dia-' mine, 5,5'-methylene-bis-benzotriazole and salts of salicye alaminoguanidine.

- As with the compound of formula I, any further additive is advantageously employed in a proportion within the range of from 0.01%to 5% by weight, based on the weight of untreated organic materials. a

In combination with an antioxidant suitable for use in EXAMPL "1 A mixture of 17.4 parts of adipic'acid dihydra zide and 31 parts of triacetonarnine in parts of methanolwas,

heated under reflux conditions for 12 hours. On removal:

of the methanol by distillation under reduced pressure, a white solid was left which was recrystallised from ethanol to give 42 parts of di-(2,2,6,6-tetramethylpiperidinyl- 4) adipoyl-di-hydrazone as a white solid. This product had a melting point of 212 C. and the following elemental analysis by weight:

' Calculated (for Found cziHuNe fl Carbon 64. 03 64. 22 Hydrogen 9. 90 9. 89 Nitrogen- 18. 85 18. 74

EXAMPLE 2 The procedure described in Example 1 was followed except that the adipic acid dihydrazide was replaced by 23 parts of sebacic acid dihydrazide.

In this way, there were produced 25 parts of di-(2,2,6,6- tetrame thylpiperidinyl-4) sebacoyl di-hydrazone having melting-point of 195 to 197 C. and the following elemental analysis by weight:

Calculated (for Found Cas azNe z) Carbon.. 66.87 66. 62 Hydrogen- 10. 56 10.39 Nitrogen. 16. 51 16. 66

EXAMPLE 3 The procedure described in Example 1 was followed, but the adipic acid dihydrazide was replaced by 206 parts thiodipropionic acid dihydrazide.

In this way, there were produced 20.3 parts of di-(2,2,6, G-tetramethylpiperidinyl-4) thiopropionyl di-hydrazone having melting range of 192 to 195 C. and the following elemental analysis by weight:

Calculated (for Found C 24H44Nu0 a S) Carbon 57.35 59. 98 Hydrogen. 9. 29 9. 23 Nitrogen 17. 34 17. 50 Sulphur 6. 86 6. 66

EXAMPLE 4 A mixture of 7.4 parts of acetic acid hydrazide and 15.5 parts of triacetonamine in 80 parts of methanol was heated under reflux conditions for 12 hours. On removal of the methanol by distillation under reduced pressure, a white solid was left which was recrystallised from ethyl acetate to give 16.5'parts of 2,2,6,6-tetramethylpiperidinyl-4- acetyl hydrazone as a white solid having a melting point of 149-150 C. and the following elemental analysis by weight:

Calculated (for Found Cu u s Carbon..-- 62.99 62.56 Hydrogen. 10.34 9.95 Nitrogen 19. 95 19. 91

EXAMPLE. 5

A mixture of 21.6 parts of heptanoic acid hydrazide and 23.25.parts,of triacet'onamine in 150 parts of methanol was heated under reflux conditions for 24 hours. On

removal of the methanol by distillation under reduced press uirea white .solidwas left. which was recrystallised from absolute ethyl alcohol tofgiye 21 parts of 2,2,6,6 tetramethyl-4-heptanoyl hydrazone having a melting point 6 of 69-71 C. and the following elemental analysis by weight:

' Calculated (for Found iu nNzO) Carbon 68. 40 68. 30 Hydrogen 10. 83 11.05 Nitrogen 14. 66 14.

EXAMPLE 6 A mixture of 27.0 parts of lauric acid hydrazide and 18.3 parts of triacetonamine in 300 parts of methanol Was heated under reflux conditions for 12 hours. On removal of the methanol by distillation under reduced pressure a white waxy solid remained. This solid was dissolved in ether and filtered to remove trace quantities of the lauric acid hydrazide, the ether was removed by distillation under reduced pressure to give 2,2,6,6-tetramethylpiperidinyl-4-lauroyl hydrazone having the following elemental analysis by weight:

Calculated (for Found Cn n sO) Carbon 72. 18 71. 74 Hydrogen 11. 8O 11. 75 Nitrogen 11. 76 11.95

EXAMPLE 7 A mixture of 2.98 parts of stearic acid hydrazide and 2.33 parts of triacetonamine were heated under reflux in parts of toluene for 36 hours, the water formed in the reaction being removed using a Dean and Stark apparatus. On removal of the toluene by distillation under reduced pressure, a white solid was left which was recrystallised from methanol to give 1.10 parts of 2,2,6,6- tetramethylpiperidinyl-4-stearoyl hydrazone having a melting point of 72-3- C. and the following elemental analysis by weight:

Calculated (for Carbon... 74. 46 74. 50 Hydrogen 12. 18 12. 20 Nitrogen 9. 58 9. 64

EXAMPLE 8 Calculated (for Found caoHaoN or) Carbon 67. 66 67. 62 Hydrogen 10. 69 10. 59 Nitrogen 15. 52 15. 78

EXAMPLE 9 A mixture of 20.4 parts of isobutyr icacid hydrazide. and 81.0 parts of triacetonamine in parts of methanol 1 was heated under refluxconditions for 2 hours. On cooling the solution a white solid crystallised out which was collected by filtration and then recrystallised from methanol to give 25.2 parts of 2,2,6,6-tetramethylpiperidinyl-4-isobutyroyl hydrazone as white needles having a melting point of 164-5 C. and the following elemental analysis by weight.

Calculated (for Found C HzN5O) Carbon 65. 42 65. 20 Hydrogen 10. 64 10. 45 Nitrogen 17. 37 17. 55

EXAMPLE A mixture of 13.6 parts of benzoic acid hydrazide and 15.5 parts of triacetonamine in 100 parts of methanol was heated under reflux conditions for hours. On removal of methanol by distillation under reduced pressure, a white solid was left which was recrystallised from l00120 C. petroleum ether to give 2,2,6,6-tetramethylpiperidinyl-4-benzoyl hydrazone having a melting point of 194-5" C. and the following elemental analysis by weight.

Calculated (for Found Cm n a Carbon 70. 59 70. 33 Hydrogen 8. 72 8. 42 Nitrogen 15. 59 15.

EXAMPLE 1 l A mixture of 24.9 parts of p-toluic acid hydrazide and 31.0 parts of triacetonamine in 500 parts of ethanol was heated under reflux conditions for 24 hours. On removal of the ethanol by distillation under reduced pressure, a white solid was left which was recrystallised from I00- 120 C. petroleum ether to give 20.6 parts of 2,2,6,6- tetramethylpiperidinyl-4-p-toluoyl hydrazone having a melting point of 187-8 C. with decomposition and the following elemental analysis by weight.

Calculated (for Found C17H2NZ0) Carbon. 70. 92 71. 05 Hydrogen 8. 56 8. 77 Nitrogen 14. 82 14. 62

EXAMPLE 12 A mixture of 9.70 parts of isophthalic acid hydrazide and 31.0 parts of triacetonamine in 100 parts of methanol was heated under reflux conditions for 24 hours. On cooling a white solid crystallised from the solution, which was collected by filtration, and recrystallised from methanol to give 10.0 parts of di-(2,2,6,6-tetramethylpiperidinyl-4) isophthaloyl-di-hydrazone having a melting point of 240-1 C. with decomposition and the following elemental analysis by weight.

Calculated (for Found C2u 40 sOz) Carbon 66. 52 66. 80 Hydrogen 8. 69 8. Nitrogen 17. 70 17. 90

EXAMPLE 13 I Calculated (tor I I Found CzeHzsNa l Carbon 74. 67 74.27 Hydrogen 8. 04 7. 79 12. 98 12.99

' Nitrogen 8 EXAMPLE 14 A mixture of 22.40 parts of phenylacetic acid hydrazide and 31.0 parts of triacetonamine in 500 parts of ethanol was heated under reflux conditions for 24 hours. On removal of the ethanol by distillation under reduced pressure, a white solid was left which was recrystallised from acetone to give 32.80 parts of 2,2,6,6-tetramethylpiperidinyl-4-phenylacetyl hydrazone having a melting point of 1589 C. and the following elemental analysis by weight.

Calculated (for Found (CuHzr a Carbon 71. 23 71.05 Hydrogen. S. 83 8. 77 Nitrogen 14. 8O 14. 62

EXAMPLE 15 a I A mixture of 10.0 parts of a-naphthylacetic acid hydra zide and 11.62 parts of triacetonamine in 150 parts of methanol was heated under reflux conditions for 24 hours. On removal of the methanol by distillation under reduced pressure, a white solid was left which was recrystallised from acetone to give 11.20 parts of 2,2,6,6-tetramethylpiperidiny1-4-a-naphthylacetyl hydrazone having a melting point of 196-7 C. and the following elemental analysis by weight.

Calculated (for Found CzrHnNaO) Carbon 74. 51 74. 72 Hydrogen 7. 99 B. 06 Nitrogen 12. 39 12. 46

EXAMPLE 16 A mixture of 4.53 parts of a,a-diphenylacetic acid hydrazide and 4.65 parts of triacetonamine in 75 parts of methanol was heated under reflux conditions for 24 hours. On cooling the solution a white solid separated out which was collected by filtration and recrystallised from methanol to give 1.50 parts of 2,2,6,6-tetramethylpiperidinyl-4- u,a-diphenylacetyl hydrazone having a melting point of 216-17 C. and the following elemental analysis by weight.

Calculated (for Found CflaHzqNaO) Carbon 75. 60 76. oo Hydrogen 8. 06 8. 04 Nitrogen 11. 78 11. 56

EXAMPLE 17 A mixture of 9.90 parts of cyclohexane carboxylic acid hydrazide and 10.85 parts of triacetonamine in parts of methanol was heated under reflux conditions for 24 hours. On removal of the methanol by distillation under reduced pressure, a white solid was left which was recrystallised from benzene to give 13.20 parts of 2,2,6,6-tetramethylpiperidinyl-4-cyclohexane carboxyl hydrazone as a white solid having a melting point of 194-5 C. and the following elemental analysis by weight.

Calculated (101' Found C aHznNzO) Carbon 69. 35 69. 10 Hydrogen 10. 45 10. 05 Nitrogen 15. 19 15. 10

EXAMPLE 18 A mixture of 6.80 parts of formic acid hydrazideand 23.0 parts of triacetonamine in 150 parts of methanol was heated under reflux conditions for 12 hours. On removal of the methanol by distillation under reduced pressure, a solid was left which was recrystallised from ethanol to give 2,2,6,6-tetramethylpiperidinyl-4-formyl hydrazone as a Calculated (for Found CiuH1o a) Carbon 61.17, 60.88 Hydrogen 9.99 9.71 Nitrogen 21.34 21. 30

' EXAMPLE -19 A mixture of 23.0 parts of'isocaproic acid, 100 parts of methanol and 1.0 part of concentrated sulphuric acid were heated under reflux conditions for 18 hours. The solution was cooled and 11.0 parts of hydrazine hydrate were added and the solution refluxed for a further 24 hours. The solution'was cooled and a small amount of a white crystalline solid was filtered off. To the'filtrate was added 28.17 parts of triacetonamine and the solution was heated under reflux conditions for a further 24 hours. On removing the methanol by distillation under reduced pressure, a solid was left which was recrystallised from ethyl acetate to give 17.80 parts of 2,2,6,6-tetramethylpiperidinyl-4 isocaproyl hydrazone as a white solid having a melting point of 128.5 9.5 C. and the following elemental analysis by weight.

' Calculated (for Found Cn n a Carbon 67. 80 67. 40 Hydrogen 11. 08 10. 93 Nitrogen... 15. 94 15. 71

EXAMPLES 20 AND 21 Yellowness factor: M 400 (560) wherein A T represents the transmission losses at the wavelengths 420 and 680 mm. respectively after an exposure of 1000 h. in the Xenotest apparatus and wherein T660) represents the transmission value of an unexposed sample at a wavelength of 560 mm.

' TABLE Yellowness factor of crystal polystyrene plaques after 1,000 11. exposure in a Xenotest apparatus Yellowness factor Example No. Additive Control.

Compound of Example 9 of B.P. 1,196,224. Compolgrgd of Example No. 37" of OS Compound of Example No. 3 of BF. 1,202,298. (Ex. 2) of present invention.

(Ex. of present invention.

Similar results were obtained using the products of Examples 7, 8 and 10.

EXAMPLES 22 TO 24 A 0.15% weight/volume solution of the product of Example 1 in acetone was made up and 40 parts by volume of this solution was added to 40 parts by weight of powdered polypropylene which was substantially free from stabilising additives. A further 60 parts by volume of acetone was then added to form a slurry which was hand mixed to ensure homogeneity. The solvent was then removed by evaporation in an oven maintained at 80 C.

14 parts by weight of the dried powder were weighed into a mould measuring 6 x 6 x 0.015 inch. The mould and polishing plate were then heated in the press under constant pressure for 5 minutes. A pressure of 20 tons per square inch was applied for one minute, cooling was commenced and pressure increased so that when the temperature reached 150 C. the pressure was tons per square inch. Cooling was continued until the temperature of the mould reached 50 C. and the mould was released from the press.

The moulded sheet so obtained was exposed to light irradiation in a fademeter device consisting of a circular bank of 28 alternate sunlight and blacklight lamps. The sunlight lamps were 2 feet long 20-watt fluorescent lamps and were characterised by having a peak emission of 3000 Angstrom units and blacklight lamps were 2 feet long 40-watt ultra-violet lamps and were characterised by having a peak emission of 3,500 Angstrom units. The samples were rotated concentrically about the bank of lamps so that the radiation therefrom was uniformly distributed over the moulded sheet.

The exposed sample was examined periodically and bent through 180 C. and the time at which it snapped due to embrittlement was noted.

An oven ageing test was also carried out on strips (6.0 x 1.0 inch) of the moulded sheet in an air circulating oven maintained at C. The time taken for the test strip to fail by cracking on flexing the sample through 180 was noted.

Similar tests were carried out on polypropylene samples containing, respectively, no stabiliser and the products of Examples -1, 2 and 3. The results achieved are set out in the following table.

4) thiopropionyl di-hydrazone.

A mixture of 31.20 parts of p-t-butylbenzoic acid hydrazide and 31.0 parts of triacetonamine in 500 parts of ethanol was heated under reflux conditions for 24 hours. On removal of the ethanol by distillation under pressure, a white solid was left, which was recrystallised twice from ethyl acetate to give 1380 parts of 2,2,6,6-tetramethyl piperidinyl-4-p-t-butylbenzoyl hydrazone having a melting point of --166 C. and the following elemental analysis by weight:

Calculated (for Found CzoHn sO) Carbon 73. 46 72. 99 Hydrogen 9. 54 9. 46 Nitrogen. 12. 52 12. 74

EXAMPLE 26 A mixture of 15.80 parts of 2-ethy1hexanoic acid hydrazide and 23.0 parts of triacetonamine in 250 parts of methanol were heated under reflux conditions for 15 hours. On removing the methanol by distillation under reduced pressure a reddish oil was left which slowly solidified; two recrystallisations from ethanol gave 7. 10 parts of 2,2,6,6-tetramethylpiperidinyl-4-2-ethylhexanoyl hydrazone as a white solid having a melting point of 9193 C. and the following elemental analysis by weight:

Calculated (for Found CnHazNaO) Carbon 69. 42 69. 11 Hydrogen 11.38 11. 26 Nitrogen 14. 02 14. 22

1 1 We claim: 1. A compound having the formula CH3 CH3 C-GH: HN\ /G=N.NH.%.R

C-CH: CH3 OH; I

and their acid salts, wherein R represents hydrogen, a straightor branched-alkyl having from 1 to 20 carbon atoms in which the alkyl chain may be uninterrupted or interrupted by one sulphur atom; a cycloalkyl having from 5 to 12 carbon atoms, a cycloalkylalkyl having from 6 to 12 carbon atoms, phenyl, naphthyl, a phenyl or naphthyl substituted alkyl containing from 7 to 14 carbon atoms, an alkyl substituted phenyl having from 7 to i14 carbon atoms or R represents the grouping of formula 01% /CH; /CH2-C om-o CH3 CH: 11

wherein Y is a divalent, straightor branched-chain alkylone having from '1 to '20 carbon atoms in which the alkylene chain is uninterrupted or interrupted by one sulphur atom; or a phenyl or naphthyl arylene having from 6 to CH -C GHQ-C CH3 CH: III

2. *A compound according to claim 1, wherein 'R is hydrogen, an alkyl residue having 1 to 17 carbon atoms, cyclohexyl, an aral kyl residue having from 7 to 14 carbon atoms, phenyl, alkylphenyl having from 7 to carbon atoms, naphthyl, or R has the formula II as defined in claim 1 wherein Y is an alkylene residue having 4 to 10 carbon atoms uninterrupted or interrupted by one sulphur atom or Y is phenylene and wherein a is l.

3. A compound according to claim 1, wherein R is an alkyl residue having from 1 to 12 carbon atoms, a cycloalkyl residue having 6 carbon atoms, a cycloalkyl alkyl or phenyl or naphthyl substituted alkyl residue from 7 to 11 carbon atotms, or an alkyl substituted phenyl residue having from 7 to 10 carbon atoms, or R has the formula tH as defined in claim 1 wherein Y is an .al'kylene residue having from *1 to '10 carbon atoms or an rarylene having 6 carbon atoms and wherein a is l.

4. A compound according to claim 1, wherein the compound is a phosphate, carbonate, sulphate, chloride, citrate, acetate, stearate, maleate, oxalate or benzoate salt.

5. A compound according to claim 1, which is di (2,2, 6,6-tetramethylpiperidinyl-4) adipoyl dihydrazone.

'6. (A compound according to claim 1, which is di-(2,2, 6,6-te'tramethylpiperidinyl-4) sebacoyl dihydrazone.

7. A compound according to claim 1, which is ell-(2,2, 6,6 tetramethylpiperidinyl 4) thiodipropionyl di-hydrazone.

8. A compound according to claim 1, which is 2,'2,6,6- tetramethylpiperidinyl-4-formyl hydrazone.

9. A compound according to claim 1, which is 2,2,6,6- tetramethylpiperidinyl-4-acetal hydrazone.

10. A compound according to claim 1, which is 2,2,6,6- tetramethylpiperidinyl-4-isocaproyl hydrazone. h

11. A compound according to claim 1, which is 2,2,6,6- tetramethylpiperidinyl-4-heptanoyl hydrazone. v

12. A compound according to claim 1, which is2,2,6,6- tetramethylpiperidinyl-4-lauroyl hydrazone. I

13. A compound according to claim 1, which is 2,2,6,6- tetramethy1piperidinyl-4-stearoyl vhydrazone.

14. A compound according to claim 1, whichis 2,2,6,6- tetramethylpiperidinylt-isobutyroyl hydrazone.

15. A compound according to claim 1, which is 2,25,6- tetramethylpiperidinyl-4-benzoyl hydrazone.

16. A compound according to claim 1, which tetramethylpiperidinyl i-p-toluoyl hydrazone, U

17. A compound according to claim 1, which is 2,2,6,6 tetramethylpiperidinyl t-a-naphthoyl hydrazone.

18. A compound according to claim 1 which is 2,2,6,6- tetramethylpiperidiny1-4-phenylacetyl hydrazone.

19. A compound according to claim 1, which is 2,266 tetramethylpiperid-inyl-4-a-naphthylacetyl hydrazone.

20. A compound according to claim 1, which is 2,2,6,6- tetramethylpiperidinyl-4-a,u-diphenylacetyl hydrazone.

21. A compound according to claim 1, which is 2,2,6,6- te-tramethylpiperidinyll-cyclohexane carboxyl hydrazone.

22. A compound according to claim 1, which is di-(2, 2, 6,6-tetramethylpiperidinyl-4) isophthaloyl d'i-hydrazone.

23. A compound according to claim 1, which is (ii-(2,2, 6,6-tetramethylpiperidinyl-4) dodecane-1:l0-dioyl di hydrazone.

24. A compound according to claim 1, which is 2,'2,6,6- tetramethylpiperidinyl=4-p-t-butylbenzyl hydrazone.

25. A compound according to claim 1, which is 2,2,6,6- tetramethylpiperidinyl-4-2-ethylhexanoyl hydrazone.

References Cited OTHER REFERENCES Anderson et al., Chem. Abstracts 50:15944c.

G. THOMAS TODD, Primary examiner us. or. XJR. *260-45.8 N, 293.63, 293.64, 293.65, 293.76, 293.77, 

